Manufacture of yarns and the like



claims:

Patented Aug. 15, 1950 ii'annurno'ronn or YARNS'AND THE LIKE Benjamin Collins, Swarthmore, Pa., assignor to American Viscose Corporation,

De-L, a corporation of Delaware Wilmington,

No Drawing. 'Application Jurie'f27,x1944, Serial No. 542,431, which is a division of application :SeriaLNo. 389,325, April 19, 1941, now Patent No. 2,359,7 19, dated October 10, 1944. Divided and this application May 28, 1947, Serial No..

v This" inventionrelates to improvements in the manufacture of synthetic yarns, filaments, films and the like. More particularly, the invention relates to improvements in the spinning operation employedin the manufacture of synthetic yarns, filaments, films and the like from viscose. This application is a, division of my copending application Serial No. 542,431, filed June 27, 1944, now abandoned which is'in turn adivision of my application Serial No. 389,325, filed April 19, 1941, now Patent 2,359,749, datedOctober 10, 1944. M F ,Inthe manufacture of synthetic shaped articles Such as yarns, filaments, films and the like from viscose, a solution is generally first prepared of the viscose to comprise the article. The article is formed or spunby" extruding the solution through a spinneret or jet, usually'made of metal, having a minute opening or ope'nings into a coag ulating or precipitating medium. (During: the spinning operationiobstructionstend to form in the minute openings in" the spinneret or jet and they; become fouled or clogged; This results, in the case of yarn or filament spinning'jin a lack of uniformity'in the filament sizes and weak and broken filaments in the finished product and, in thecase of producing films, in a lack of uniformity in thickness. "In order to avoid these difficulties it is the present practice to inspect the spinnerets or jets at short intervals of time and replace those in which the openings have become fouled. This interrupts the continuity of the spinning operation and causes delays which are time-consuming and costly. I j v (This invention has for'its principal object to provide improvements; in the spinning operation employed in the manufacture of synthetic shaped articles such as yarns, filaments, films. and the Other objects, or the invention will bea parent.

from the following description and". appended .It has now been found that foulingof the spin- 9'Claims. (or. 18-54) or in the spinning solution, all of the chain-forming atoms in the compound consisting ofcarbon and oxygen. Generally, the greater the extent to which the compound is hydrophobic, the larger the number of oxyethylene units that are required 1 to render the compound sufficiently soluble for nerets and the need forfrequent. inspection and I replacement and the lack of uniformity in. yarns, filaments and films can be; largely eliminatedsby extruding the spinning solution in the presence of a small amount 'of .a surface active, nonionogenic organic compound of, essentially-alt phatic character and-comprising at least one hydrophobic group having a; hydrocarbonchain of at least 8 carbon atomsand a hydrophilic polyoxyethylene content of at least 8 oxyethylene units, this contentlin any particular case being sufficient to ,render the compound water-soluble sow he t is readi y o u l n. h ..spinning;ba

the purposes of the invention.

In general, the compounds contemplated by the invention are the polyethylene glycol ethers of organic compounds having at least one functional aliphatic hydroxyl group and containing at least one hydrophobic group comprising a hydrocarbon chain of at least 8 carbon atoms, such as alcohols and polyhydric alcohols, hydroxy carboxylic acids, hydroxy esters, epoxy alcohols and hydroxy epoxy esters; polyethylene glycol esters of compounds having at least one functional aliphatic carboxyl group and containing at least one hydrophobic group comprising a hydrocarbon chain of at least 8 carbon atoms, such as fatty acids, polycarbox-ylic acids, hydroxy fatty acids, and epoxy fatty acids; polyethylene glycol acetals of organic com pounds having at least one functional aliphatic aldehyde group and containing at least one hydrophobic group comprising a hydrocarbon chain of at least 8 carbon atoms, such as aliphatic aldehydes, and polyethylene glycol ether-esters, ether-acetals, ester-acetals or ether-ester-acetals of organic compounds having various combinations of hydroxyl, aldehyde, and carboxyl groups and containing at least one hydrophobic group comprising a hydrocarbon chain of at least 8 carbon atoms, such as hydroxy fatty acids, polyhydroxy fatty acids, aldoses, and -ur0nic acids. The compounds are non-ionogenic, relatively chemically unreactive, substantially stable under spinning conditions, and contain no functional groups other than ether (0x0), ester, acetal, aliphatic hydroxyl and carbonyl groups which are substantially stable under the conditions of spinning.- The stability herein referred to is such stability that the compounds, prior to their complete decomposition in the spinning solution or the spinning bath, will exert their favorable influence in preventing clogging of the openings in the spinnerets and in thereby maintaining uniformity of filament size.

The following are examplesof specific compounds that may be used in carrying out this invention: i Caprylic acid esters of polyoxyethylene glycols Pelargonic acid esters of polyoxyethylene glycols Capric acid esters of polyoxyethylene glycols Lauric acid esters of polyoxyethylene glycols V Polyoxyethylene glycol ethers of mannitan mono- Pol'yosyethylene glycol ethers of mann-itol acyl pa ia e er H s a so Polyox yethylene glycol ethers of: sorbitol acyl Vs r le c r ,s v c Polyoxyethylene glycol ethers of hexitan acyl partial esters V Polyoxyethylene glycol ethersof man-nitan acyl partial-esters i Polyoayethylene glycol ethers of sorbitan acylf .u fi ls Y Polyoxyethylene glycol ethers of hexide acyl partial esters V V g l Polyoxyethylene glycol ethers of mannide acyl. r partial esters V, M v V Pol-yoxyethylene glycol ethers of sorbideac-yl 'parw tial esters 7 g M Polyoxyethylene glycol ethers of cyclotol acyl partial esters H Polyoxyethylene glycol ethers of inositolacyl partial esters p Po-lyoxyethylene glycol ethers of monosaecha-ride acyl partial esters p 7 Polyoxyethylene glycol ethers of oligosacc'haride acyl partial esters More -specific combinations are: I V Polyoxyethyleneglycol ethersof mannitan monov laurate V v p Polyoxyethylene glycol ethers of sorbi tan monolaurate Polyoxyethylene glycol ethers of sorbitan monoleate Pblyoxyethylene glycol ethers .of mannitanmonomyristate gonic,-cap'ric, 1auric, myristic, palmitic, margaric, stearic; 1

oleic, 1icin'oleic, and hydroxy stearic.

palmitate Polyoxyethylene glycol ethers ofcmannitan mono- .i r eii Polyoxyethylehe glycol ethers of niannitan monooleate Bolyoxyethylene glycol ethers of triricinolein eoiyexytnyleiie glycol acetals of lauric aldehyde 'I l'ie polyethylene glycol group or groups may iie ciine 'cted tlre same compound by either or Both ether and ester groups depending upon the parent; substances from which they are derived and: the of producing the compounds t erefrom For example, if ricinoleic acid, hyd r y s e acid or other bi-iunctional compounds are re te" with ethylene oxide, part of the oxyethyle'rie'" units may replace the hydrogen oi the hydroxyl group while another part may replace the hydrogen of the carboxyl group, thereby prod-ucipg polyoxyethylene ether-esters.

It should be noted tha't all'of the" oxyethylene units may e; in single chairior' they may" be present in the compound in the form of two or more chains; the: mar situation being common when the compound isprod'uced by reacting ethylene. oxide vvith a parent. S mar-meaning at least two; functional groups wheth hydroxyl, aldehyde,vcarboxy1f6r ny emanation of these threeis only essential that the total number of oxyethylene units the one or more chains add up toa; total or" at least eight and sufiicierit. in any particular case to render the compound soluble the Viscose the. acid cdagiiiat'mg bath.

I Son'ie bran: ofthe oxyethylene units or chains ofsuch units mayhave either oi Both of their ends connectedl to the remaindrbf tme compound througl'i ether -ester or acetal linkages-.-

v The common methodis of making the compound with yhich th invention is concerned generally result in the formation of mixtures of compounds having a'greater or less number of oxyethylene units per molecule andanal-ytical de-- terminations ct such complex mixtures indicate the averagenumber of such units per molecule throughout the mass of the compound analyzed. Forthis reason the compounds employed in accordance with this invention may comprise molecules containing lessthan 8 oxyethyleneunits in admixture with others containing 8 or moresuch units; Accordingly, in: the specification and the claims the definition of these compounds is i'ntended to include not only thosehavi'ng a uniform and constant constitution throughout but also such complex mixtures as have'an' efiective portion containing at leaste oxyethylne units per molecule.

The various surface active compounds maybe produced any suitable manner; Generally, theymay be produced? by'feaoting ethylene oxide with the selected fatty acid, alcohol, hydroxy fatty acid, hydroiy' may acid ester" or related compound within' the-scope of the general class described above-:- For example, the reaction products "of ethylene oxidewith sorbita'n nion'o- Iauratemaybeprepared by introducingsorbitan monolaurate with a; small amount of sodium niethyl'ait asfai catalyst into a stirring autoclave and raising the to peratu'ze to gradually adding etllylii oxldto this-mixture and maintaining the temperature Between 6. and C; For reasons stated akiove, thedegree to which the reaction with the ethylene oxide is carried out depends upon the compound with which it is reacted and the character of the spinning solution or precipitating bath in which it is to be used. The reaction is carried out to such a degree that the reaction products are soluble in the spinning bath or spinning solution in which they are used.

The invention is applicable in forming regenerated cellulose shaped articles by extruding viscose solution into an acid precipitating bath, especially those containing sulfuric acid, and is found particularly advantageous where the precipitating bath contains a high concentration of metallic salts, especially zinc, in concentrations of the order of 3% to 10%.

In carrying out the invention a small amount of the surface active material of the order of 0.01 to 0.05% may be dissolvedin the spinning solution and the spinning solution is extruded into a precipitating medium. Where a liquid precipitating medium or bath is used, a small amount of the surface active material of the same order may be dissolved in the precipitating medium or may be added to both the spinning solution and the precipitating medium.

The following examples are illustrative of the invention:

Example 1.-A multifilament regenerated cellulose yarn is formed by extruding viscose solution through a spinneret into an aqueous sulfuric acid spinning bath containing a high concentration of zinc sulfate of the order of 5% and between 0.02 and 0.03% of organic compounds comprising a mannitan monolaurate having at least 1 hydroxy polyoxyethylene group per molecule and an average oxyethylene content of 20 oxyethylene units per molecule.

Example 2.A multifilament regenerated cellulose yarn is formed by extruding viscose solution through a spinneret into an aqueous sulfuric acid spinning bath containing a high concentration of zinc sulfate of the order of 5% and between 0.02 and 0.03% of organic compounds comprising a mannitan monopalmitate having at least 1 hydroxy polyoxyethylene group per molecule and an average oxyethylene content of 20 oxyethylene units per molecule.

Example 3.--A multifilament regenerated cellulose yarn is formed by extruding a viscose solution through a spinneret into an aqueous sulfuric acid spinning bath containing a high concentration of zinc sulfate of the order of 5% and between 0.02 and 0.03% of organic compounds comprising an acetal of lauric aldehyde having an average oxyethylene content of 20 oxyethylene units per molecule.

Example 4.'-A multifilament regenerated cellulose yarn is formed by extruding a viscose solution containing about 0.03% of an acetal of lauric aldehyde having an average of oxyethylene units per molecule through a spinneret into an aqueous sulfuric acid spinning bath containing a high concentration of zinc sulfate of the order of 5%.

It was found that in carrying out the spinning operation in accordance with the present invention it is necessary to change less than 50% as many spinnerets as where ordinary methods of spinning are followed. Where multifilament yarn is formed the filaments are of uniform cross-section and the yarn is of generally improved quality.

While preferred embodiments of the invention have been shown, it is to be understood that changes and variations may be made without departing from the spirit and scope of the invention as defined by the appended claims.

I claim:

1. The methodof forming artificial filaments comprising extruding viscose into an aqueous acid coagulating liquid in the presence of a small amount of a dissolved, substantially stable, surface-active non-ionogenic acetal of apolyethylene glycol containing a hydrophobic group comprising a hydrocarbon chain of at least 8 carbon atoms and containing at least 8 oxyethylene units per molecule and a sufficient number of such units in excess of eight to render the compound substantially soluble in the viscose solution.

2. The method of claim 1 in which the acetal is present in the viscose spinning solution.

3. The method of claim 1 in which the acetal is present in the coagulating liquid.

4. The method of claim 1 in which the acetal is present in both the. viscose and coagulating liquid.

5. The method of claim 1 in which the acetal is that derived from lauric aldehyde.

6. A viscose spinning solution containing a small amount of a dissolved, substantially stable, surface-active non-ionogenic acetal of a polyethylene glycol containing a hydrophobic group comprising a hydrocarbon chain of at least 8 carbon atoms and containing at least 8 oxyethylene units per molecule and a sufiicient number of such units in excess of eight to render the compound substantially soluble in the viscose solution.

7. An aqueous liquid for coagulating viscose solutions, said liquid comprising an acid and a small amount of a dissolved, substantially stable, surface-active non-ionogenic acetal of a polyethylene glycol containing a hydrophobic group comprising a hydrocarbon chain of at least 8 carbon atoms and containing at least 8 oxyethyl ene units per molecule and a sufiicient number of such units in excess of eight to render the compound substantially soluble in the viscose solution.

8. The viscose of claim 6 in which the acetal is that derived from lauric aldehyde.

9. The coagulating liquid of claim 7 in which the acetal is that derived from lauric aldehyde.

BENJAMIN W. COLLINS.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,970,578 Schoeller Aug. 21, 1934 2,069,336 Schmidt et al. Feb. 2, 1937 2,125,031 Polak July 26, 1938 2,359,749 Collins Oct. 10, 1944 2,359,750 Collins Oct. 10, 1944 

1. THE METHOD OF FORMING ARTIFICAL FLAMENTS COMPRISING EXTRUDING FISCOSE INTO AN AQUEOUS ACID COAGULATING LIQUID IN THE PRESENCE OF A SMALL AMOUNT OF A DISSOLVED, SUBSTANTIALLY STABLE SURFACE-ACTIVE NON-IONOGENIC ACETAL OF A POLYETHYLENE GLYCOL CONTAINING A HYDROPHOBIC GROUP COMPRISING A HYDROCARBON CHAIN OF AT LEAST 8 CARBON ATOMS AND CONTAINING AT LEAST 8 OXYETHYLENE UNITS PER MOLECULE AND A SUFFICIENT NUMBER OF SUCH UNITS IN EXCESS OF EIGHT TO RENDER THE COMPOUND SUBSTANTIALLY SOLUBLE IN THE VISCOSE SOLUTION. 